Quaternary ammonium salts and process of making the same



Patented Oct. 19.45

QUATERNABY AMMONIUM S AL'I'S AND PROCESS OF MAKING THE SAME Maurice Arthur Thoroid Rogers, Blackley, Man- .chester, England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain r UNITED STATES PATENT ol-"nca N Drawing. Original application August 2, 1939, Serial No. 288.059. Divided and this application April 23, 1940, Serial No. 331,189.

. Britain August 2, 1938 This application is a division of my copending application Serial No. 288,059, filed August 2,

The present invention relates to the manufacture of new quaternary ammonium" compounds which are useful in treating textile materials, especially for the purpose of conferring waterrepellent properties thereon.

According to the invention we make new quaternary ammonium salts by causing a halogenomethyl compound of the formula wherein R is an aliphatic radical of at least 7 carbon atoms, X is a'halogen and A is a divalent organic radical, to react with an aliphatic or heterocyclic tertiary amine.

As will be seen from-the formula, the halogenomethyl compounds which are used as starting materials are derivatives of the fatty alcohols ROH. They are, in fact, conveniently made by interaction of two molecular proportions of the chloroformic ester of the alcohol ROH with one molecular proportion of a diamine NHa-A-NHa, whereby a dicarbamate of formula isvobtained, followed by treatment of the said dicarbamate with formaldehyde (or a polymer thereof) and a hydrogen halide or a substance behaving as such under the conditions of the reaction (e. g. phosgene), or'with a product of the interaction of formaldehyde and a hydrogen halide, namely a dihalogenodimethyl ether.

Then as suitable fatty alcohols for making the halogenomethyl compounds there may be mentioned, for example, octyl, decl, dodecyl, myristyl, cetyl, octadecenyl, octadecyl and ceryl alcohols and mixtures of these and similar alcohols obtained by reduction of the acids of natural fats and oils e. g.- coconut oil, palm kernel oil or wool fat, alcohols obtainable by reduction of the estrs of montanic acid, alcohols obtainable by hydrolysis of the mixed sulphuric esters which are formed by sulphonation of polymerised lower olefines and also alcohols which are likewise esters such, for example, as p-hydroxyethyl stearate.

Thus as suitable halogenomethyl compounds to be used in the process of the invention there may be mentioned, for example,pdi-octadecyl N:N-'di- (chloromethyl) -ethylenedicarbamate,-

di-octadecyl NzN' di' (chloromethyl) hexamethylenedicarbamate, d1 octadecyl N:N' diand di- (bromomethyl) -dicarbamates.

In amt 7 Claims. (01. 260- 295),

(chloromethyl) p phenylenedicarbamate. di-

octadecyl N:N '-di-(chloromethyl) m phenylenedicarbomate, di-octadecyl N:N'-di (chloromethyl) -o-phenylenedicarbamate, di-octadecyl N:N'-di-(chloromethyl)' 1:5 naphthylenedicarbamate, di-octadecyl N:N'-di- (chloromethyl) 2 methoxy-lz4 phenylenedicarbamate, di-octadecyl NzN' di-(chloromethyl) -2-chloro-l:4- phenylenedicarbamate, di octadecyl NzN' di- (chloromethyl) -6 methyl-izii-phenylenedicarbamate, the di-(chloromethyl) dicarbamates having the formulae respectively.

CuHi-r-0C0 OsO-N-oo-o-omn H101 onnt-o-c 0- OsoQ-l -c o-o-cunn 'Lmci cum and CHIC! UHaOl and also the corresponding di-(bromomethyD- dicarbamates and the corresponding di-dodecyl, di-cetyl, and di-montanyl di-(chloromethyD- or by applying external cooling means.

The new quaternary salts are white or pale coloured solids which are soluble in water, benzene; alcohol, chloroform and ethylene dichloride and sparingly soluble in ether and acetone.

Their aqueous solutions are viscous and foam slightly on shaking but when they are boiled the foaming power is gradually lost and the quaternary salt is decomposed. When the quaternary I v CH| CH] n I U c n o-c o-I OCHrOT-C 0-0-CnHu All thesalts themselves are heated above 100 C. they decompose, forming water-insolublewaxy substances.

- A of our novel series of compoundsis their adaptability of being applied to textile materials, which are of animal or vegetable origin or which are composed of regenerated cellulose or. of cellulose esters or ethers, to give them properties of softness, or of softness and water-repelience, which are re- The product may be purified if necessary by dissolving it in cold' chloroform, filtering the solution if necessary, and adding dry acetone, which brings about a precipitation. The white 5 solid so obtained is filtered off and washed with sistant to laundering ordry-cleaning treatments.

The starting out material for this example is made as follows:

35 parts .(i. e. /50 mol) of di-octadecyl pphenylene-dicarbamate of the formula C aHa-r0CONI iCsHa(p)-' v.

I (M. P. 146? Camade by condensing two molec- I ular proportions of octadecyl chloroformate with one molecular proportion of p-phenylenediamine) and 6 parts of paraformaldehyde (i. e.

mol) are mixed with 500 parts of benzene.

The mixture is stirred and heated. The temdry acetone. It dissolves in water on warming forming clear viscous' solutions which foam slightly on shaking. It is also soluble in benzene, chloroform and methyl and ethyl alcohols.

In a similar manner, starting in each case with 1 molecular proportion of the corresponding dicarbamic acid dialkyl ester, 2 molecular proportions of formaldehyde. and 2.5 molecular proportions of pyridine, there may be made the following dlpyridinium dichlorides, namely, dl-octadecyl NzN" di (chloropyridinium-methyl) -mphe'nylenedicarbalnate, di-octadecyl N:N'-di- (chloropyridinium methyl) -o-phenylenedicarbamate, di octadecyl N:N'-di-(chloropyridinium methyl) S-methyl-l:3-phenylenedicarbamate, di-octadecyl N:N'-di- (chloropyridiniummethyl) 2 chloro-1:4-phenylenedicarbamate,

di-dodecyl N:N'-di- (chloropyridinium-methyi) p-phenylenedicarbamate, di-octadecyl NzN'edi- (chloropyridinium methyl) ethylenedicarbamate, di octadecyiv N:N'-di-(chioropyridi-.

' -nium-methyl)'-hexamethylenedicarbamate, and di octadecyl N:N' di (chloropyridiniumperature is kept at 60 C. while dry hydrogen chloride is passed in. As the reaction proceeds water separates out and the liquid becomes turbid. Eventually the liquid becomes clear again and the water separates from it and forms a separate'layer. -Theloweraqueous layer is then run to waste. The benzene is distilled oil from phenylenedicarbamate of the formula:

. ICn n0 C0NCHaCl Cn u-0-C 0- -03.01 It' is an oil, which on standing at room temperature, or on cooling to below room temperature,

enedicarbamate of the formula:

' onnro-co-mcmNwrnocl mm-o-co-n-cmmcmi-on methyl) -methyienedicarbamate.

ExampleZ parts of di-octadecyl m phenylenedicarbamate (M. P. 96 C., made by condensing two molecular proportions of octadecyl chloroformate with one molccularproportion of mphenylenediamine) are converted into the dichloromethyl compound by the method described,

in respect'of the p-lsomer, in Example 1.

The di-octadecyl N:N'-di-(chloromethyi)-mphenylenedicarbamate so obtained is dissolved,

in 150 parts of benzene. The solution is cooled to below 10 C. and stirred and 20 parts of triethylamine are gradually added during 1 hour. The

- cooling and stirrin'g are continued for a further 16 h urs. 600 t th the upper layer, preferably under sub-'atmos- 45 0 parts of ace one are en added pheric pressure. The residue left in the still is di octadecyl N N'-di-(chloromethyl)-p-.

whereby the quaternary Salt is precipitated. It is filtered ofl and dried.

Dl-qctadecyl N:N'- dl (triethylchloroammoniummethyi) -m-phenylenedicarbamate is thus obtained in the form of a white powder. It dissolves in water, forming clear viscous solutions which foam slightly on shaking. It is also soluble in benzene, ethanol and chloroform; it is insolub in ether.

'If in this, process there are used, instead of he 35 parts of di-octadecyl m-phenylenedicar bamate,'33 of dl-octadecyl ethylenedicarbainate, there is similarly obtained di-octadecyl N:N di (triethylchloroammoniummethyl) ethylenedicarbamate. This compound likewise is obtained as a white powder which dissolves in water, forming clear viscous solutions which foam slightly onshaking, and which is soluble also in benzene, chloroform and ethanol.

If in either of the above processes, instead of adding to the solution of the dichloromethyi compound 20 parts of triethylamine, 12 parts of trimethylaminc are'passed in and the product is then worked up as described, there is obtained N :N'- di -(trimethylohloroammonium-methyl) -m-phenylenedicarbamate or dioctadecyl NzN -di-(trimethylchloroammoniummethyD- ethylenedicarbamate; These compounds have properties similar to those of their triethylammonium analogues.

di (cyclohexyl dimethyl chloroammonium decantation with ethyl acetate and then with dry acetone. On prolonged standing in an evacuated vessel it solidifies and is then ground to a powder. It is a pale yellow, slightly hygroscopic solid which dissolves in water, forming solutions which foam slightly. It is also soluble in benzene, chloroform and trichloroethylene.

I claim:

i. Quaternary ammonium salts, useful as water-repellent agents, of the formula 3-0-0 o-N-cHr-Nacm-x R-OC0-I'Q'CHr-N(tert)-X wherein R is an aliphatic radical of at least '7 carbon atoms, X is a halogen, A is a divalent organic radical selected from the group consist- .methyl)-p-phenylenedicarbamate separates out i in the form of a viscous oil. This iswashed by.

. 3 Quaternary ammonium salts. useful as water-repellent agents, of the formula wherein a is an aliphatic radical of at least '1 carbon atoms, x is a halogen, A is an alky ene radical and N(tert) stands for a member of he group consisting of aliphatic and heterocycli tertiary amines. Y 4. Process for the manufacture of new quater nary ammonium salts which comprises causing a" halogenomethyl compound of the formula R-O-CO-N-GHr-X i R-0 C0-I ICHrX wherein R is an aliphatic radical of at least '4 carbon atoms, X is a halogen and A is an alkylene v amines.

ing of aliphatic and aromatic radicals free of organic radical selected from the will W of aliphatic and free of substituents which'are reactivctoward formalde hyde. to combine with a member of the group consisting of aliphatic and heterocyclic tertiary amines.

5. Quaternary ammonium salts, useful as we ter-repellency agents, of the formula wherein R is an aliphatic radical of at least '7 carbon atoms, A is an alkylehe radical and N(C5Hs) stands for the pyridine radical.

6. Process for the manufacture of quaternary H ammonium salts which comprises causing a chicromethyl compound of the formula carbon atoms and A is an alkylene radical, to

\ combine with pyridine.

' 7. Quaternary ammonium compounds having the formula:

ao-co-N-cnrNacm- -x '50 in whichR-isan aliphatic radical of at least '1 carbon atoms, X is a halogen, A is an alkylene radical and N(tert) is a aliphatic amine.

ARTHUR THOROLD ROGERS.

Patent No. 2,386,142. 7 October 2, 1945.

, MAURICE ARTHUR THOROLD ROGERS It is hereby certified that errors appear in the printed specification of the ebove numbered (patent requiring correction as follows: Page 1, first column, line 39, for "-de'clirea decyl; and second column, lines 22 to 25 inclusive, for that portion of the formula'reading' on, I cm we C 1 read As; that the said Letters Patent should he read with these glorections therein that the same may conform to the record of the case in the Patent ce. v

' I Signed and sealed this 18th day of December, A. D. 1945.

LESLIE FRAZER, First Assistant Commissioner of PM. 

